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. Author manuscript; available in PMC: 2026 Feb 27.
Published in final edited form as: J Am Chem Soc. 2025 Dec 30;148(1):2078. doi: 10.1021/jacs.5c21238

Correction to “Synthesis of Bicyclo[2.1.0]pentanes and Vinylcyclopropanes Using Palladium Carbenes: Ligand-Controlled Carbene Reactivity”

Isaiah K Eckart-Frank 1, Emily S Arnold 1, Liam P Murphy 1, Sidney M Wilkerson-Hill 1
PMCID: PMC12937139  NIHMSID: NIHMS2133848  PMID: 41468398

The identity of NHC-adduct 10 was reported incorrectly in Figure 5 in the original publication (as well as in the Supporting Information) as a carbon addition adduct of IPr into tosyl hydrazone substrate 1b, affording an alkenyl diazene. Additional {1H,13C} HSQC and {1H, 13C} HMBC studies conducted in our group revealed that compound 10 is instead the azine adduct formed by addition of IPr into the terminal Natom of the diazo intermediate formed from the base-mediated decomposition of 1b. The observed 1H NMR signal at 6.87 ppm (s, 1H) correlates to a carbon with a 13C NMR signal of 152.8 ppm (carbon circled in blue for compound 10 in Figure 5) by {1H,13C} HSQC, which is in line with other reports of these adducts.1 Additionally, {1H,13C} HMBC data reveal a three-bond 1H–13C correlation between the allylic methylene of 10 and the same carbon at 152.8 ppm, which would not be present in our originally proposed structure. A revised version of Figure 5 with the correct structure in eq 4 is included here, and Section XI of the Supporting Information has been corrected.

Figure 5.

Figure 5.

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Independently synthesized alkyl diazenes do not react with Pd(0)-NHC catalysts to give housanes. N-Heterocyclic carbenes react with hydrazones to form azine adducts. Dipp = 2,6-diisopropylphenyl.

We are thankful to Prof. Jean Bouffard (Ewha Woman’s University) for bringing this mistake to our attention. This misassignment does not change any conclusions regarding the unwanted reactivity of NHC ligands with our hydrazones substrates. This unwanted reactivity negatively impacts catalysis as discussed in the original publication.

Supplementary Material

Supporting Information

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.5c21238.

  • Experimental details, additional experimental results, and compound characterization (PDF)

REFERENCES

  • (1).(a) Wei S; Li S; Chen C; He Z; Du X; Wang L; Zhang C; Wang Q; Pu L Access to Fluorescent Azines from N-Heterocyclic Carbene Precursors and NTosylhydrazones. Adv. Synth. Catal 2017, 359, 1825–1830. [Google Scholar]; (b) Guo R; Zheng Y; Ma J Electrophilic Reaction of 2,2,2-Trifluorodiazoethane with the in Situ Generated N-Heterocyclic Carbenes: Access to N-Aminoguanidines. Org. Lett 2016, 18, 4170–4173. [DOI] [PubMed] [Google Scholar]

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Supplementary Materials

Supporting Information
NIHMS2133848-supplement-Supporting_Information.pdf (318.5KB, pdf)

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